Method of reducing crop damage

ABSTRACT

The present invention relates to a method of reducing crop damage by treating the seed of the crop with the safener before sowing. This can be done in addition to the use of crop protection combinations/compositions, in particular herbicide/safener combinations and compositions comprising thereof, which are highly suitable to protect crops from herbicide damage in pre- and post-emergence treatments.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the National Stage entry of InternationalApplication No. PCT/EP2019/054667, filed 26 Feb. 2019, which claimspriority to European Patent Application No. 18159140.5, filed 28 Feb.2018.

BACKGROUND Field

The invention relates to a method of reducing crop damage by treatingthe seed of the crop with the safener before sowing. This can be done inaddition to the use of crop protection combinations/compositions, inparticular herbicide/safener combinations and compositions comprisingthereof, which are highly suitable to protect crops from herbicidedamage in pre- and post-emergence treatments.

Description of Related Art

Aclonifen (compound I) is known as pre- and post ermergence herbicidefor a long time and is active against a broad weed spectrum mainly invegetables.

However, some herbicides or combinations thereof are not fullycompatible with a number of important crop plants, such as, for example,various cereal species (such as wheat, triticale, barley, rye), sugarcane, sugar beet, soybeans, oilseed rape, corn, rice, potatoes,vegetables or cotton and cause crop damage. Accordingly, in some crops,they cannot be used in a way that ensures the desired broad herbicidalactivity against harmful plants without causing damage to the crop.

Some agrochemicals can reduce crop damage when used in combination withherbicides. These compounds are referred to as safeners and are widelyused in crop protection, particularly in the field of weed controlduring application of herbicides in crops. The mode of action ofsafeners is often not known in detail and their efficacy generallydepends on the crop and on the specific herbicide to be combined with.

SUMMARY

It was an object of the present invention to provide a method forfurther reducing crop damage using known combinations of herbicides andsafeners and compositions comprising thereof. Surprisingly, this objectis achieved by the following methods/schemes of treatment:

Method A

Step 1: Treatment of the seed with a safener

Step 2: Applying aclonifen (compound I) or combinations/compositionscomprising thereof in a post-emergence treatment

Method B

Step 1: Treatment of the seed with a safener

Step 2: Applying aclonifen (compound I) or combinations/compositionscomprising thereof in a pre-emergence treatment

Method C

Step 1: Treatment of the seed with a safener

Step 2: Applying aclonifen (compound I) or combinations/compositionscomprising thereof and a safener in a post-emergence treatment

Method D

Step 1: Treatment of the seed with a safener

Step 2: Applying aclonifen (compound I) or combinations/compositionscomprising thereof and a safener in a pre-emergence treatment

Preferred are the following methods:

Method A-1

Step 1: Treatment of the seed with a safener from the group consistingof isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl andcloquintocet-mexyl including its hydrates and salts (group I)

Step 2: Applying aclonifen (compound I) in a post-emergence treatment

Method B-1

Step 1: Treatment of the seed with a safener from the group consistingof isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl andcloquintocet-mexyl including its hydrates and salts (group I)

Step 2: Applying aclonifen (compound I) in a pre-emergence treatment

Method C-1

Step 1: Treatment of the seed with a safener from the group consistingof isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl andcloquintocet-mexyl including its hydrates and salts (group I)

Step 2: Applying aclonifen (compound I) and a safener from the groupconsisting of isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl andcloquintocet-mexyl including its hydrates and salts (group I) in apost-emergence treatment.

Method D-1

Step 1: Treatment of the seed with a safener from the group consistingof isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl andcloquintocet-mexyl including its hydrates and salts (group I)

Step 2: Applying aclonifen (compound I) and a safener from the groupconsisting of isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl andcloquintocet-mexyl including its hydrates and salts (group I) in apre-emergence treatment.

More preferred are the following methods:

Method A-2

Step 1: Treatment of the seed with mefenpyr-diethyl

Step 2: Applying aclonifen (compound I) in a post-emergence treatment

Method B-2

Step 1: Treatment of the seed with mefenpyr-diethyl

Step 2: Applying aclonifen (compound I) in a pre-emergence treatment

Method C-2

Step 1: Treatment of the seed with mefenpyr-diethyl

Step 2: Applying aclonifen (compound I) and mefenpyr-diethyl in apost-emergence treatment

Method D-2

Step 1: Treatment of the seed with mefenpyr-diethyl

Step 2: Applying aclonifen (compound I) and mefenpyr-diethyl in apre-emergence treatment

Most preferred are the following methods:

Method A-3

Step 1: Treatment of the seed with mefenpyr-diethyl in an amount of 1 to0.01 g/kg

Step 2: Applying aclonifen (compound I) in a post-emergence treatment

Method B-3

Step 1: Treatment of the seed with mefenpyr-diethyl in an amount of 1 to0.01 g/kg

Step 2: Applying aclonifen (compound I) in a pre-emergence treatment

Method C-3

Step 1: Treatment of the seed with mefenpyr-diethyl in an amount of 1 to0.01 g/kg.

Step 2: Applying aclonifen (compound 1 and mefenpyr-diethyl in apost-emergence treatment

Method D-3

Step 1: Treatment of the seed with mefenpyr-diethyl in an amount of 1 to0.01 g/kg

Step 2: Applying aclonifen (compound I) and mefenpyr-diethyl in apre-emergence treatment

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT Definitions

Safener:

S1) Compounds of the group of heterocyclic carboxylic acid derivatives:

S1^(a)) Compounds of the type of dichlorophenylpyrazoline-3-carboxylicacid (S1^(a)), preferably compounds such as1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylicacid, ethyl1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate(S1-1) (“mefenpyr(-diethyl)”), and related compounds, as described inWO-A-91/07874;

S1^(b)) Derivatives of dichlorophenylpyrazolecarboxylic acid (S1^(b)),preferably compounds such as ethyl1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate(S1-4) and related compounds, as described in EP-A-333 131 and EP-A-269806;

S1^(c)) Derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1^(c)),preferably compounds such as ethyl1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and relatedcompounds, as described, for example, in EP-A-268554;

S1^(d)) Compounds of the type of triazolecarboxylic acids (S1^(d)),preferably compounds such as fenchlorazole(-ethyl), i.e. ethyl1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate(S1-7), and related compounds, as described in EP-A-174 562 and EP-A-346620;

S1^(e)) Compounds of the type of 5-benzyl- or5-phenyl-2-isoxazoline-3-carboxylic acid or5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1^(e)), preferablycompounds such as ethyl5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds, asdescribed in WO-A-91/08202, or 5,5-diphenyl-2-isoxazolinecarboxylic acid(S1-10) or ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (S1-11)(“isoxadifen-ethyl”) or n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate(S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate(S1-13), as described in the patent application WO-A-95/07897.

S2) Compounds of the group of 8-quinolinoxy derivatives (S2):

S2^(a)) Compounds of the type of 8-quinolinoxyacetic acid (S2^(a)),preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate (common name“cloquintocet-mexyl” (S2-1), 1,3-dimethyl-but-1-yl(5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl(5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxyprop-2-yl(5-chloro-8-quinolinoxy)acetate (S2-4), ethyl(5-chloro-8-quinolinoxy)acetate (S2-5), methyl(5-chloro-8-quinolinoxy)acetate (S2-6), allyl(5-chloro-8-quinolinoxy)acetate (S2-7), 2-(2-propylideneiminoxy)-1-ethyl(5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxo-prop-1-yl(5-chloro-8-quinolinoxy)acetate (2-9) and related compounds, asdescribed in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492366, and also (5-chloro-8-quinolinoxy)acetic acid (2-10), its hydratesand salts, for example its lithium, sodium, potassium, calcium,magnesium, aluminium, iron, ammonium, quaternary ammonium, sulphonium orphosphonium salts, as described in WO-A-2002/34048;

S2^(b)) Compounds of the type of (5-chloro-8-quinolinoxy)malonic acid(S2^(b)), preferably compounds such as diethyl(5-chloro-8-quinolinoxy)malonate, diallyl(5-chloro-8-quinolinoxy)malonate, methyl ethyl(5-chloro-8-quinolinoxy)malonate and related compounds, as described inEP-A-0 582 198.

S3) Active compounds of the type of dichloroacetamides (S3) which arefrequently used as pre-emergence safeners (soil-acting safeners), suchas, for example, “dichlormid” (N,N-diallyl-2,2-dichloroacetamide)(S3-1), “R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine)(S3-2), “R-28725” (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine)(S3-3), “benoxacor”(4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),“PPG-1292” (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide)(S35), “DKA-24”(N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) (S3-6),“AD-67” or “MON 4660” (3-dichloroacetyl-1-oxa-3-aza-spiro[4,5]decane)(S3-7), “TI-35” (1-dichloroacetylazepane) (S3-8) “diclonon” (dicyclonon)(S3-9)((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one),furilazole” or “MON 13900”((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10), andalso its (R)-isomer (S3-11).

S4) Compounds of the class of acylsulphonamides (S4):

S4^(a)) N-acylsulphonamides of the formula (S4^(a)) and salts thereof,as described in WO-A-97/45016

-   -   in which    -   R_(A) ¹ is (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, where the 2        last-mentioned radicals are substituted by v_(A) substituents        from the group consisting of halogen, (C₁-C₄)-alkoxy,        halo-(C₁-C₆)-alkoxy and (C₁-C₄)-alkylthio and, in the case of        cyclic radicals, also (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl;    -   R_(A) ² is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, CF₃;    -   m_(A) is 1 or 2;    -   v_(D) is 0, 1, 2 or 3;

S4^(b)) Compounds of the type of 4-(benzoylsulphamoyl)benzamides of theformula (S4^(b)) and salts thereof, as described in WO-A-99/16744,

-   -   in which    -   R_(B) ¹, R_(B) ² independently of one another are hydrogen,        (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₃-C₆)-alkenyl,        (C₃-C₆)-alkynyl,    -   R_(B) ³ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl or        (C₁-C₄)-alkoxy,    -   m_(B) is 1 or 2;    -   for example those in which    -   R_(B) ¹=cyclopropyl, R_(B) ²=hydrogen and (R_(B)        ³)=2-OMe(“cyprosulfamide”, S4-1),    -   R_(B) ¹=cyclopropyl, R_(B) ²=hydrogen and (R_(B) ³)=5-Cl-2-OMe        (S4-2),    -   R_(B) ¹=ethyl, R_(B) ²=hydrogen and (R_(B) ³)=2-OMe(S4-3),    -   R_(B) ¹=isopropyl, R_(B) ²=hydrogen and (R_(B) ³)=5-Cl-2-OMe        (S4-4) and    -   R_(B) ¹=isopropyl, R_(B) ²=hydrogen and (R_(B) ³)=2-OMe (S4-5);

S4^(c)) Compounds of the class of benzoylsulphamoylphenylureas of theformula (S4^(c)) as described in EP-A-365484,

-   -   in which    -   R_(C) ¹, R_(C) ² independently of one another are hydrogen,        (C₁-C₈)-alkyl, (C₃-C₈)-cycloalkyl, (C₃-C₆)-alkenyl,        (C₃-C₆)-alkynyl,    -   R_(C) ³ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, CF₃,    -   m_(C) is 1 or 2;    -   for example    -   1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea,    -   1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea,    -   1-[4-(N-4,5-dimethylbenzoylsulphamoyl)phenyl]-3-methylurea;

S4^(d)) Compounds of the type of N-phenylsulphonylterephthalamides ofthe formula (S4^(d)) and salts thereof, which are known, for example,from CN 101838227,

-   -   in which    -   R_(D) ⁴ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, CF₃;    -   m_(D) is 1 or 2;    -   R_(D) ⁵ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,        (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₅-C₆)-cycloalkenyl.

S5) Active compounds from the class of hydroxyaromatics andaromatic-aliphatic carboxylic acid derivatives (S5), for example ethyl3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid,3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclicacid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described inWO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.

S6) Active compounds from the class of 1,2-dihydroquinoxalin-2-ones(S6), for example 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one,1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione,1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-onehydrochloride,1-(2-methylsulphonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one,as described in WO-A-2005/112630.

S7) Compounds from the class of diphenylmethoxyacetic acid derivatives(S7), for example methyl diphenylmethoxyacetate (CAS-Reg. Nr.41858-19-9) (S7-1), ethyl diphenylmethoxyacetate, ordiphenylmethoxyacetic acid, as described in WO-A-98/38856.

S8) Compounds of the formula (S8), as described in WO-A-98/27049,

-   -   where the symbols and indices have the following meanings:    -   R_(D) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,        (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,    -   R_(D) ² is hydrogen or (C₁-C₄)-alkyl,    -   R_(D) ³ is hydrogen, (C₁-C₈)-alkyl, (C₂-C₄)-alkenyl,        (C₂-C₄)-alkynyl or aryl, where each of the carbon-containing        radicals mentioned above is unsubstituted or substituted by one        or more, preferably by up to three, identical or different        radicals from the group consisting of halogen and alkoxy; or        salts thereof,    -   n_(D) is an integer from 0 to 2.

S9) Active compounds from the class of3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CASReg. No.: 219479-18-2),1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CASReg. No.: 95855-00-8), as described in WO-A-1999/000020.

S10) Compounds of the formula (S10^(a)) or (S10^(b)) as described inWO-A-2007/023719 and WO-A-2007/023764

-   -   in which    -   R_(E) ¹ is halogen, (C₁-C₄)-alkyl, methoxy, nitro, cyano, CF₃,        OCF₃    -   Y_(E), Z_(E) independently of one another are O or S,    -   n_(E) is an integer from 0 to 4,    -   R_(E) ² is (C₁-C₁₆)-alkyl, (C₂-C₆)-alkenyl, (C₃-C₆)-cycloalkyl,        aryl; benzyl, halobenzyl,    -   R_(E) ³ is hydrogen or (C₁-C₆)-alkyl.

S11) Active compounds of the type of oxyimino compounds (S11), which areknown as seed dressings, such as, for example, “oxabetrinil”((Z)-1,3-dioxolan-2-ylmethoxyimino-(phenyl)acetonitrile) (S11-1), whichis known as seed dressing safener for millet against metolachlor damage,

-   -   “fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone        O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as        seed dressing safener for millet against metolachlor damage, and    -   “cyometrinil” or “CGA-43089”        ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is        known as seed dressing safener for millet against metolachlor        damage.

S12) Active compounds from the class of isothiochromanones (S12), suchas, for example, methyl[(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No.:205121-04-6) (S12-1) and related compounds from WO-A-1998/13361.

S13) One or more compounds from group (S13):

-   -   “naphthalic anhydrid” (1,8-naphthalenedicarboxylic anhydride)        (S13-1), which is known as seed dressing safener for corn        against thiocarbamate herbicide damage,    -   “fenclorim” (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is        known as safener for pretilachlor in sown rice,    -   “flurazole” (benzyl        2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3),        which is known as seed dressing safener for millet against        alachlor and metolachlor damage,    -   “CL 304415” (CAS Reg. No.: 31541-57-8)        (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4)        from American Cyanamid, which is known as safener for corn        against imidazolinone damage,    -   “MG 191” (CAS Reg. No.: 96420-72-3)        (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) which is known        as safener for corn,    -   “MG 838” (CAS Reg. No.: 133993-74-5) (2-propenyl        1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6),    -   “disulphoton” (O,O-diethyl S-2-ethylthioethyl        phosphorodithioate) (S13-7),    -   “dietholate” (O,O-diethyl O-phenyl phosphorothioate) (S13-8),    -   “mephenate” (4-chlorophenyl methylcarbamate) (S13-9).

S14) Active compounds which, besides a herbicidal effect against harmfulplants, also have a safener effect on crop plants such as rice, such as,for example, “dimepiperate” or “MY 93” (S-1-methyl-1-phenylethylpiperidine-1-carbothioate), which is known as safener for rice againstmolinate herbicide damage,

-   -   “daimuron” or “SK 23”        (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as        safener for rice against imazosulphuron herbicide damage,    -   “cumyluron”=“JC 940”        (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see        JP-A-60087254), which is known as safener for rice against some        herbicide damage,    -   “methoxyphenone” or “NK 049”        (3,3′-dimethyl-4-methoxybenzophenone), which is known as safener        for rice against some herbicide damage,    -   “CSB” (1-bromo-4-(chloromethylsulphonyl)benzene) from Kumiai        (CAS Reg. No. 54091-06-4), which is known as safener against        some herbicide damage in rice.

S15) Compounds of the formula (S15) or its tautomers,

-   -   as described in WO-A-2008/131861 and WO-A-2008/131860,    -   in which    -   R_(H) ¹ is (C₁-C₆)-haloalkyl,    -   R_(H) ² is hydrogen or halogen,    -   R_(H) ³, R_(H) ⁴ independently of one another are hydrogen,        (C₁-C₁₆)-alkyl, (C₂-C₁₆)-alkenyl or (C₂-C₁₆)-alkynyl,        -   where each of the 3 last-mentioned radicals is unsubstituted            or substituted by one or more radicals from the group            consisting of halogen, hydroxy, cyano, (C₁-C₄)-alkoxy,            (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylamino,            di-[(C₁-C₄)-alkyl]-amino, [(C₁-C₄)-alkoxy]-carbonyl,            [(C₁-C₄)-haloalkoxy]-carbonyl, unsubstituted or substituted            (C₃-C₆)-cycloalkyl, unsubstituted or substituted phenyl, and            unsubstituted or substituted heterocyclyl;    -   or (C₃-C₆)-cycloalkyl, (C₄-C₆)-cycloalkenyl, (C₃-C₆)-cycloalkyl        which is at one site of the ring condensed with a 4 to        6-membered saturated or unsaturated carbocyclic ring, or        (C₄-C₆)-cycloalkenyl which is at one site of the ring condensed        with a 4 to 6-membered saturated or unsaturated carbocyclic        ring,        -   where each of the 4 last-mentioned radicals is unsubstituted            or substituted by one or more radicals from the group            consisting of halogen, hydroxy, cyano, (C₁-C₄)-alkyl,            (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,            (C₁-C₄)-alkylthio, (C₁-C₄)-alkylamino,            di-(C₁-C₄)-alkyl]-amino, [(C₁-C₄)-alkoxy]-carbonyl,            [(C₁-C₄)-haloalkoxy]-carbonyl, unsubstituted or substituted            (C₃-C₆)-cycloalkyl, unsubstituted or substituted phenyl, and            unsubstituted or substituted heterocyclyl; or    -   R_(H) ³ is (C₁-C₄)-alkoxy, (C₂-C₄)-alkenyloxy,        (C₂-C₆)-alkynyloxy or (C₂-C₄)-haloalkoxy, and    -   R_(H) ⁴ is hydrogen or (C₁-C₄)-alkyl, or    -   R_(H) ³ and R_(H) ⁴ together with the directly bound N-atom are        a 4 to 8-membered heterocyclic ring, which can contain further        hetero ring atoms besides the N-atom, preferably up to two        further hetero ring atoms from the group consisting of N, O and        S, and which is unsubstituted or substituted by one or more        radicals from the group consisting of halogen, cyano, nitro,        (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,        (C₁-C₄)-haloalkoxy, and (C₁-C₄)-alkylthio.

Preferred safener are:

Isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl andcloquintocet-mexyl including its hydrates and salts, for example itslithium, sodium, potassium, calcium, magnesium, aluminium, iron,ammonium, quaternary ammonium, sulphonium or phosphonium salts (groupI).

Seed:

Seed of crop plants, such as, for example, various cereal species (suchas wheat, triticale, barley, rye), sugar cane, sugar beet, soybeans,oilseed rape, corn, potatoes, vegetables, rice or cotton.

Preferred is the seed of the following crop plants: wheat, triticale,barley, rye corn, rice.

Combinations:

Combinations according to the invention are: aclonifen (compound I) andat least one or more herbicides from the group consisting of:2-(2,4-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone, bromoxynil,bromoxynil-butyrate, -potassium, -heptanoate, and -octanoate,benzofenap, butachlor, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium,-diolamin, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl,-isopropylammonium, -potassium, -triisopropanolammonium, and -trolamine,bicyclopyrone, cinmethylin, diflufenican, dimethenamid, ethoxysulfuron,fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl,fenquinotrione, fentrazamide, florasulam, florpyrauxifen-benzyl,flufenacet, fluroxypyr, fluroxypyr-meptyl, foramsulfuron, iodosulfuron,iodosulfuron-methyl-sodium, isoproturon, isoxaflutole, lancotrione,mefenacet, mesosulfuron, mesosulfuron-methyl, metolachlor,S-metolachlor, metribuzin, metosulam, nicosulfuron, oxadiargyl,oxadiazon, pethoxamid, prosulfocarb, pyrasulfotole, pyroxasulfone,pyroxsulam, tefuryltrione, tembotrione, thiencarbazone,thiencarbazone-methyl, tolpyralate, and triafamone, pendimethalin,propoxycarbazone, halauxifen-methyl, 2-methyl-4-chlorophenoxyacetic acid(group II).

Composition

Compositions within the context of the present invention comprise inaddition to the combinations according to the invention one or morefurther component(s) selected from the group consisting of formulationauxiliaries, additives customary in crop protection, and furtheragrochemically active compounds.

Additives

Additives are for example, fertilizers and colorants.

Agrochemically Active Compounds

Agrochemically active compounds are for example fungicides andinsecticides.

Preferred among the agrochemically active compounds are prothioconazole,tebuconazole, fluoxastrobin, difenoconazole, penflufen, fluopicolide,fludioxonil, thiodicarb, triticonazole, prochloraz, fluxapyroxad,thiodicarb, imidacloprid, clothianidin, flupyradifurone, picarbutrazox,mefenoxam, flonicamid, ipconazole, diniconazole, metconazole, sithiofam,pyraclostrobin, carboxin, sedaxane, thiamethoxam, tefluthrin,cypermethrin, metalaxyl,N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide,Bacillus subtilis and Bacillus firmus.

Especially preferred among the agrochemically active compounds areprothioconazole, tebuconazole, difenoconazole, fludioxonil,triticonazole, imidacloprid, clothianidin, ipconazole, sithiofam,sedaxane, thiamethoxam, metalaxyl andN-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide.

The use of compound I or of the combinations/compositions according tothe invention provides for excellent herbicidal effectiveness against abroad spectrum of economically important mono- and dicotyledonous annualweeds and perennial weeds.

The present invention therefore provides a method of controllingundesired plants or for regulating the growth of plants, preferably inplant crops, in which the compound I or the combinations/compositionsaccording to the invention are applied to the plants (e.g. mono- ordicotyledonous weeds or undesired crop plants) or the area on which theplants grow. The compound I or the combinations/compositions accordingto the invention can be applied at different growth stages (GS) of theplant allowing broadening of the applicability of the compound I or thecombinations/compositions according to the invention, and providing foran efficient method of controlling undesired weeds or plants atdifferent growth stages. Examples of mono- and dicotyledonous weed florawhich can be controlled by the compound I or thecombinations/compositions according to the invention, without alimitation to certain species being intended through the naming, are:

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis,Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina,Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis,Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera,Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum,Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, andSorghum.

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia,Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella,Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura,Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium,Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria,Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago,Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex,Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea,Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, andXanthium.

Pre-emergence treatment: If the compound I or thecombinations/compositions according to the invention are applied to thesoil's surface prior to weed emergence, then either the weed seedlingsare prevented completely from emerging, or the weeds grow to seedlingstage, but then their growth stops and finally, after three to fourweeks, they die completely.

For the use as post-emergence application of the compound I or thecombinations/compositions according to the invention to the green partsof the plants, weed growth is likewise inhibited following treatment, orthey die completely after a certain time, so that in this mannercompetition by the weeds, which is harmful to the crop plants, iseliminated very early on and in a lasting manner.

The compound I or combinations/compositions according to the inventioncan thus effectively be applied as pre- or post-emergence applicationfor controlling undesired weed plant growth, preferably in crops such ascereals, maize, and rice. Combinations/compositions according to theinvention comprising the safener Isoxadifen-ethyl can preferably beapplied as post-emergence application in maize and rice;combinations/compositions according to the invention comprising thesafener Mefenpyr-diethyl can preferably be applied as post-emergenceapplication in cereals, naming without limitation wheat, rye, triticale,barley; and combinations/compositions according to the inventioncomprising the safener Cyprosulfamide or Isoxadifen-ethyl can preferablybe applied as post-emergence application in maize.

The method according to the invention can also be used for controllingharmful weeds in crops of genetically modified plants or in crops ofplants being modified by conventional mutagenesis. As a rule, thetransgenic plants are distinguished by particularly advantageousproperties, for example by resistances to certain pesticides, primarilycertain herbicides, resistances to plant diseases/pathogens or insectsor microorganisms such as fungi, bacteria or viruses. Other particularproperties relate, for example, to the harvested material with respectto quantity, quality, storability, composition and specific ingredients.

Combinations or compositions according to the invention can be producedby known methods, for example as mixed formulations of the individualcomponents, optionally with further active ingredients, adjuvants and/orcustomary formulation assistants.

In the combinations or compositions of the invention, the applicationrate of compound I is customarily 10 to 1000 g of active ingredient (a.i.) per hectare, preferably 50 to 600 g a. i./ha, especially preferably100 to 450 g a. i./ha. The application rate of the further activeingredient of group II is customarily 1 to 3000 g of active ingredientper hectare, preferably 2,5 to 2500 g a. i./ha, especially preferably 4to 1000 g a. i./ha. However, the weight ratios of individual componentscan be varied within relatively wide ranges. Generally speaking, thereare 1:240 to 200:1 parts by weight, preferably 1:40 to 50:1 parts byweight, especially preferably 1:10 to 40:1 of component I per part byweight of component of group II.

In step 1 the seed is treated with a safener. The amount ranges from 1to 0.01 g/kg, preferably from 1 to 0.1 g/kg, most preferably from 0.75to 0.25 g/kg. The sowing density varies from 75 to 150 kg seeds/ha(depending on the variety and the sowing date).

Considering the lowest sowing density of 75 kg/ha, 0.75 to 75 gsafener/ha are applied to the field when sowing the seeds prepared instep 1.

Considering the highest sowing density of 150 kg/ha, 1.5 to 150 gsafener/ha are applied to the field when sowing the seeds prepared instep 1.

For method C/C-1/C-2/C-3 and D/D-1/D-2/D-3 in step 2 the applicationrate of safener is 1 to 1000 g safener/ha, preferably 5 to 500 gsafener/ha, most preferably 50 to 350 g safener/ha.

EXAMPLES

1. Method as Used in the Prior Art

For the Untreated control, wheat seeds (winter wheat, TRZAW) were placedin sandy loam soil in pots of a diameter of 7 cm, covered with soil andcultivated in a greenhouse under good growth conditions.

Post-emergence application was done when the plants had reached growthstage BBCH11 (BBCH is the international coding system for the growthstage of crops and weeds).

The herbicide (Compound I) was formulated as suspension concentrate(SC).

The safener (mefenpyr-diethyl) was formulated as wettable powder (WP).

The compounds were sprayed onto the green parts of the plants as anaqueous suspension at an equivalent water application rate of 300 l/ha.

The combination of herbicide and safener was applied as a tank mix.

After application, the test plants were kept in the greenhouse undergood growth conditions. 14 days after application, % crop damageobserved on the treated plants was scored visually in comparison tountreated controls.

Values in the table below are mean values from at least 3 replicates.

Safener Safener dosage Herbicide dosage in in seed % dosage tank mixtreatment crop Treatment (g/ha) (g/ha) (g/kg) damage Herbicide post-em.1500 — — 17 Herbicide post-em. + 1500 200 — 8 Safener in tank mixUntreated — — — 02. Method A

For the Untreated control, wheat seeds (winter wheat, TRZAW) were placedin sandy loam soil in pots of a diameter of 7 cm, covered with soil andcultivated in a greenhouse under good growth conditions.

For the safener seed treatment, sufficient seeds were weighed into screwtop glass bottles approximately twice the volume of the seeds.

The safener (mefenpyr-diethyl, formulated as suspension concentrate(SC)) was weighed out so that the required rates (g a.i./kg seed) wouldbe obtained, dissolved in water (1 ml water per 10 g of seeds), andadded to the seeds to produce a slurry.

The bottles were capped and then placed in an overhead shaker (set atmedium speed for up to 1 hour) so that the seeds were evenly coated withthe slurry. The bottles were uncapped and the seeds were sown asdescribed above.

For the seed treatment process, the blind formulation (the SCformulation without the safener mefenpyr-diethyl) was used as seedtreatment as described above.

Post-emergence application of the herbicide was done when the plants hadreached growth stage BBCH11.

The herbicide (Compound 1) was formulated as suspension concentrate (SC)and was sprayed onto the green parts of the plants as an aqueoussuspension at an equivalent water application rate of 300 l/ha.

After application, the test plants were kept in the greenhouse undergood growth conditions. 14 days after application, % crop damageobserved on the treated plants was scored visually in comparison tountreated controls.

Values in the table below are mean values from at least 3 replicates.

Safener Safener dosage Herbicide dosage in in seed % dosage tank mixtreatment crop Treatment (g/ha) (g/ha) (g/kg) damage Herbicide post-em.1500 — — 17 Safener seed treatment + 1500 — 0.5 2 Herbicide post-em.Safener seed treatment — — 0.5 0 Seed treatment process — — — 0Untreated — — — 03. Method C

For the Untreated control, wheat seeds (winter wheat, TRZAW) were placedin sandy loam soil in pots of a diameter of 7 cm, covered with soil andcultivated in a greenhouse under good growth conditions.

For the safener seed treatment, sufficient seeds were weighed into screwtop glass bottles approximately twice the volume of the seeds.

The safener (mefenpyr-diethyl, formulated as suspension concentrate(SC)) was weighed out so that the required rates (g a.i./kg seed) wouldbe obtained, dissolved in water (1 ml water per 10 g of seeds), andadded to the seeds to produce a slurry.

The bottles were capped and then placed in an overhead shaker (set atmedium speed for up to 1 hour) so that the seeds were evenly coated withthe slurry. The bottles were uncapped and the seeds were sown asdescribed above.

For the seed treatment process, the blind formulation (the SCformulation without the safener mefenpyr-diethyl) was used as seedtreatment as described above.

Post-emergence application was done when the plants had reached growthstage BBCH11.

The herbicide (Compound I) was formulated as suspension concentrate(SC).

The safener (mefenpyr-diethyl) was formulated as wettable powder (WP).

The compounds were sprayed onto the green parts of the plants as anaqueous suspension at an equivalent water application rate of 300 l/ha.

The combination of herbicide and safener was applied as a tank mix.

After application, the test plants were kept in the greenhouse undergood growth conditions. 14 days after application, % crop damageobserved on the treated plants was scored visually in comparison tountreated controls.

Values in the table below are mean values from at least 3 replicates.

Safener Safener dosage Herbicide dosage in in seed % dosage tank mixtreatment crop Treatment (g/ha) (g/ha) (g/kg) damage Herbicide post-em.1500 — — 17 Safener seed treatment + 1500 200 0.5 2 Herbicide post-em. +Safener in tank mix Safener in tank mix — 200 — 5 Safener seed treatment— — 0.5 0 Seed treatment process — — — 0 Untreated — — — 04. Method D

For the Untreated control, wheat seeds (winter wheat, TRZAW) were placedin sandy loam soil in pots of a diameter of 7 cm, covered with soil andcultivated in a greenhouse under good growth conditions.

For the safener seed treatment, sufficient seeds were weighed into screwtop glass bottles approximately twice the volume of the seeds.

The safener (mefenpyr-diethyl, formulated as suspension concentrate(SC)) was weighed out so that the required rates (g a.i./kg seed) wouldbe obtained, dissolved in water (1 ml water per 10 g of seeds), andadded to the seeds to produce a slurry.

The bottles were capped and then placed in an overhead shaker (set atmedium speed for up to 1 hour) so that the seeds were evenly coated withthe slurry. The bottles were uncapped and the seeds were sown asdescribed above.

For the seed treatment process, the blind formulation (the SCformulation without the safener mefenpyr-diethyl) was used as seedtreatment as described above.

For the pre-emergence application, the herbicide (Compound I) wasformulated as suspension concentrate (SC), the safener(mefenpyr-diethyl) was formulated as wettable powder (WP).

The compounds were sprayed to the soil surface as an aqueous suspensionat an equivalent water application rate of 300 l/ha.

The combination of herbicide and safener was applied as a tank mix.

After application, the test plants were kept in the greenhouse undergood growth conditions. 14 days after application, % crop damageobserved on the treated plants was scored visually in comparison tountreated controls.

Values in the table below are mean values from at least 3 replicates.

Safener Safener dosage Herbicide dosage in in seed % dosage tank mixtreatment crop Treatment (g/ha) (g/ha) (g/kg) damage Herbicide pre-em.1000 — — 12 Herbicide pre-em. + 1000 200 — 18 Safener in tank mixSafener seed treatment + 1000 — 0.5 3 Herbicide pre-em. Safener seedtreatment + 1000 200 0.5 1 Herbicide pre-em. + Safener in tank mixSafener in tank mix — 200 — 5 Safener seed treatment — — 0.5 2 Seedtreatment process — — — 0 Untreated — — — 0

The invention claimed is:
 1. A method of reducing crop damage in winterwheat (TRZAW), comprising treating seed of the crop with a safenerbefore sowing (1) and applying aclonifen (compound I) orcombinations/compositions comprising thereof and a safener in apre-emergence treatment (2), wherein the safener is mefenpyr-diethyl. 2.The Method according to claim 1 wherein the composition in 2 comprisesin addition to said compound I, at least one further herbicide selectedfrom the group consisting of:2-(2,4-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone, bromoxynil,bromoxynil-butyrate, -potassium, -heptanoate, and -octanoate,benzofenap, butachlor, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium,-diolamin, -ethyl, -2-ethylhexyl, -isobutyl, -isoctyl,-isopropylammonium, -potassium, -triisopropanolammonium, and -trolamine,bicyclopyrone, cinmethylin, diflufenican, dimethenamid, ethoxysulfuron,fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl,fenquinotrione, fentrazamide, florasulam, florpyrauxifen-benzyl,flufenacet, fluroxypyr, fluroxypyr-meptyl, foramsulfuron, iodosulfuron,iodosulfuron-methyl-sodium, isoproturon, isoxaflutole, lancotrione,mefenacet, mesosulfuron, mesosulfuron-methyl, metolachlor,S-metolachlor, metribuzin, metosulam, nicosulfuron, oxadiargyl,oxadiazon, pethoxamid, prosulfocarb, pyrasulfotole, pyroxasulfone,pyroxsulam, tefuryltrione, tembotrione, thiencarbazone,thiencarbazone-methyl, tolpyralate, and triafamone, pendimethalin,propoxycarbazone, halauxifen-methyl, 2-methyl-4-chlorophenoxyacetic acid(group II).
 3. The Method according to claim 1 wherein the crop is agenetically modified plant.